EP0314944B1 - Finishing composition and process for the treatment of fiber materials - Google Patents

Description

The present invention describes aqueous finishing agents for the soft hydrophobic / oleophobic treatment of fiber materials based on perfluoroaliphatic compositions and extenders. A method for soft hydrophobic / oleophobic treatment is also claimed.

The water, oil and dirt repellent finish with fluorochemical agents or compositions has long been known (see Chwala / Anger "Handbook of Textile Aids", 1977, Verlag Chemie, Weinheim, pages 470 ff). A major disadvantage of this equipment is its high price. So so-called extenders were soon developed in order to reduce the cost of this equipment first and later and also to obtain improvements in terms of convenience. First, metal salt-containing paraffin emulsions, fat-modified synthetic resins, waxes and similar products were used for this purpose, but all of these cannot convince when evaluating the sum of the effects. The addition products of olefins, vinyl and allyl esters of aliphatic straight-chain or branched-chain acids on hydrogen polysiloxanes (US-A 4 004 059) brought about an improvement in water and oil repellency, but were not yet completely convincing in view of the permanences required today and, especially with regard to the desired soft-hand effect, were also able to achieve the same Not meet requirements.

Finishing agents have now been found which can be used for the simultaneous particularly smooth and soft hydrophobic / oleophobic treatment of fiber materials. These finishing agents contain perfluoroaliphatic group-containing hydrophobic / oleophobic agents, selected polyethylene emulsions and fluorine-free soft handle extender emulsions in selected proportions.

The finishing agents of this invention, namely the perfluoroaliphatic group-containing agent, the polyethylene emulsion and the fluorine-free polysiloxane softener extender are either available as a finished formulation or are added individually to the finishing bath. In this way, finishing agents are created which, surprisingly, are distinguished by overall very good effects, which also have excellent washing and dry cleaning resistance. The present invention therefore describes in claims 1 to 10 aqueous finishing agents for the soft hydrophobic / oleophobic treatment of fiber materials. A method for the soft hydrophobic / oleophobic treatment of the fiber materials is then claimed in claims 11 to 13.

Ingredient A) is a hydrophobic / oleophobic agent containing perfluoroaliphatic groups, many of which are commercially available and which in the finished formulation have at least 5% by weight, in particular 5.5 to 15% by weight, very particularly preferably 7 to Contain 12% by weight fluorine. The perfluoroaliphatic group R _f can be straight-chain, branched-chain or, if the length is appropriate, also cyclic be. Combinations of these are of course also conceivable for R _f . The basic structure of the perfluoroaliphatic radical can contain oxygen and / or trivalent nitrogen heteroatoms in the chain, bound only to carbon atoms. These types of fluoroaliphatic agents are well known to those skilled in the art and he will have no difficulty in using the useful products.
The following are examples:
The reaction of perfluoroaliphatic thioglycols with diisocyanates results in polyurethanes containing perfluoroaliphatic groups. These products are typically used in aqueous dispersion for fiber treatment. Such reaction products are described, for example, in US Pat. No. 4,054,592.

Another group of compounds in component A) are N-methylol condensation products containing perfluoroaliphatic groups. These compounds also belong to the prior art and are described in US Pat. No. 4,477,498, where the emulsification of such products is also discussed in detail.
The polycarbodiimides containing perfluoroaliphatic groups (R _f groups) are prepared, for example, by reacting perfluoroaliphatic sulfonamide alkanols with polyisocyanates in the presence of suitable catalysts. This class of compounds can also be used alone, but mostly it is used with other compounds containing R _f groups, especially together with the (co) polymers. And this addresses another group of compounds that can be used in dispersion as component A). Among these compounds, all known fluoroaliphatic radical-containing polymers can be used, with condensation polymers such as polyesters and polyamides containing corresponding perfluoroaliphatic groups, and especially (co) polymers based on, for example, R _f acrylates and R _f methacrylates, different fluorine-free vinyl compounds being used as comonomers. In DE-A-2 310 801 (see also GB-A-1.413.051 / 052) these compounds are discussed in detail with further reference to the literature, and the preparation of polycarbodiimides containing R _f groups and the mixture of these compounds with one another are dealt with in detail here .

In addition to the above-mentioned agents containing perfluoroaliphatic groups, other fluorochemical compounds can also be used as constituent A), for example guanidines containing R _f groups (US Pat. No. 4,540,479), allophanates containing R _f groups (US Pat. No. 4,606,737) and Biurete containing R _f groups (US-A 4,668,406). These classes of component A) are mostly used in combination.

As can be seen from the entire literature, the active compounds of component A) generally have one or more perfluoroaliphatic radicals with preferably at least 4, in particular 6 to 14, carbon atoms. Component A) is used in the finishing agents according to the invention in amounts of 25 to 65% by weight, based on the finishing agent. Since the components A) preferably contain about 7 to 12% by weight of fluorine, agents which have 30 to 55% by weight of these components are particularly suitable.

The emulsifiable polyethylene (polyethylene wax) contained in component B) is known and is described in detail in the prior art (DE-A-2 359 966, DE-A 2 824 716 and DE-A 1 925 993). As a rule, the emulsifiable polyethylene is one with functional groups, in particular COOH groups, which can be partially esterified. These functional groups are introduced by oxidation of the polyethylene. However, it is also possible to obtain the functionality by copolymerizing ethylene with, for example, acrylic acid. The emulsifiable polyethylenes contained in component B) have a density of at least 0.92 g / cm³ and an acid number at 20 ° C from at least 5 to. The finishing agents according to the invention are particularly preferred of those emulsifiable polyethylenes which have a density at 20 ° C. of 0.95 to 1.05 g / cm 3, an acid number of 10 to 60 and a saponification number of 15 to 80. This material is generally commercially available in the form of scales, lozenges and the like. Component B), that is to say the dispersion of the emulsifiable polyethylene, is used in the finishing agents in amounts of 10 to 35% by weight, based on the finishing agent and based on a 20 to 35% dispersion (based on polyethylene wax). It has been shown that higher amounts of component B) make the soft handle even more pleasant, flowing, even softer, so that amounts of 20 to 35% by weight of component B), based on the overall finishing agent, are particularly good are preferred.

The polyethylene wax is used in the form of emulsions. Different emulsifiers are required for this. These emulsifiers can support the soft hand effect of the finishing agents.

Modified hydrogen alkyl polysiloxanes in the form of aqueous dispersions are suitable as component C). Above all, however, compounds which are obtained by modification of hydrogen methyl polysiloxane with a long-chain alkyl radical are suitable as fluorine-free soft-grip extenders. This alkyl radical should contain an average of at least 8 carbon atoms, in particular 8 to 18 carbon atoms. This condition does not preclude the presence of low-chain alkyl radicals, but it should be noted that the average carbon chain length is at least 8 carbon atoms. Compounds of this type are described in the aforementioned US-A-4,004,059. However, those components C) which are modified to an even greater extent are particularly preferred, ie which, in addition to the above-mentioned groups, also include epoxyalkyl groups and possibly additionally aryl, in particular phenyl, groups contained in the molecule (US-A-4,625,010). Such compounds then have an Si-H content of approximately 0.02 to 6, in particular 0.3 to 1.8% by weight, an epoxy number of approximately 0.01 to 0.06 and, moreover, hydrogen per g-atom of the siloxane, at least 0.2 g atom of the same is substituted by an alkyl radical (see above).

The constituents C) are present as an average of 25 to 40% dispersions and based on these dispersions 25 to 40% by weight, in particular 25 to 35% by weight, based on the finishing agent, of the component C) are used.

These components C), like components A) and B), are prepared in a known manner (see the literature mentioned). With regard to the emulsifiers, there are basically no restrictions with regard to dispersion or dispersion polymerization, i.e. Both nonionic and conventional cationic and anionic emulsifiers can be used. However, due to the fact that the finished dispersions, that is to say the constituents A), B) and C), are mixed in the preparation of the finishing agent according to the invention and, in addition, are frequently used in combination with other constituents, it is preferred to produce more or less use non-ionic or only weakly cationic emulsifiers to keep the risk of mutual interference as low as possible. The emulsifiers that can be used individually are well known and do not require any special explanation. The emulsifiers are used in customary amounts. In general, the amount of emulsifier is 3 to 50, preferably 8 to 40,% by weight, based on the respective solid.

The finishing agents can be produced in a simple manner by combining components A) to C) in the stated amounts. These agents have the advantage of being a stable one-component finishing agent.

For the soft hydrophobic / oleophobic treatment process The fibers thus produced are used directly from fiber materials. The amounts used depend on the desired effects and are usually 40 to 100, in particular 50 to 80 g / l, based on a 25 to 35% by weight finishing agent.

As already stated above, the use of the agents according to the invention is preferred due to the presence of a one-component finishing agent. However, it is also possible in the context of the present process to prepare the usually aqueous finishing liquors with the appropriate amounts of constituents A), B) and C) and the person skilled in the art will have no trouble in achieving the desired overall effects even then. The equipment itself is carried out according to known methods.

It goes without saying that further aids customary in the textile industry can also be added to the finishing bath described above in the present process. In this context, special emphasis should be given to crease-free agents, since not only the desired crease resistance but also a further stabilization of the effects is achieved. In addition, however, fillers, flame retardants, anti-slip agents and similar products and, if necessary, the catalysts which are also necessary, all in customary amounts, are to be mentioned as additional products.

According to the present subject matter, fiber materials of all kinds can be finished as well as according to the known methods. In particular, textiles are to be mentioned as fiber materials, these textiles in turn being particularly suitable, which consist of cellulose fibers or at least partially contain cellulose fibers. In addition to cellulose, synthetic fibers such as polyester, polyamide or polyacrylonitrile fibers and wool can also be considered as additional fibers. Of course you can but the method according to the invention can also be used for finishing pure synthetic fiber and wool fiber materials. The oil and water repellent finishing of cotton / polyester blended fabrics is particularly critical and it is precisely here that the finishing agents according to the invention show their superiority over the prior art.

The advantages of the object according to the invention lie less in the oil and water repellent effects. But already when assessing the washing and cleaning persistence there are noticeable advantages over the prior art (US-A-4,004,059).

Above all, however, a clear superiority of the subject of the application can be ascertained when comparing the handle. According to the prior art, it was already possible to obtain a good to very good silicone handle due to the extenders used. However, the surface smoothness and above all the inner softness left something to be desired in this known equipment. In the present subject, all requirements are also met in this regard, so that the achievement of outstanding soft-hand effects can now be mentioned. It must be regarded as surprising that, above all, the addition of the selected component B) in the stated amounts can achieve a - albeit slight - increase in the oil- and water-repellent effects, a noticeable improvement in the permanence and, above all, a considerable positive influence on the grip is, after all, the silicone handle has been generally considered to be particularly soft and smooth. Another advantage is the stability of the effects of the present finishing agents.

The present invention is described in more detail in the examples below, parts being parts by weight and percentages being weight percent.

example 1

The following components are mixed together to produce an equipment (equipment I):

Part A 1)

55 parts of a commercially available dispersion (emulsifier: polyethoxylated quaternary ammonium salt) consisting of polymer X (see DE-A 2 310 801) and R _f polycarbodiimide emulsion (see example 1, DE-A 2 310 801) in a weight ratio of 2: 1.

Part B 1)

20 parts of a commercially available, nonionic, finely divided, aqueous 20% polyetylene wax dispersion (50% nonylphenol ethoxylated with an average of 15 moles of ethylene oxide, based on polyethylene wax, as an emulsifier; polyethylene wax with a density at 20 ° C. of about 1, an acid number of about 13 and a saponification number of about 22).

Component C 1)

35 parts of an aqueous, nonionic (emulsifier: 3% of a C₁₀-C₁₂ fatty alcohol ethoxylated with 6 moles of ethylene oxide) 35% soft-handle extender dispersion (H- and epoxy-functional aryl-methyl-C₁₂-alkyl polysiloxane with the following data: viscosity (25 ° C) approx. 1350 mPa.s, refractive index n _D ²⁵ 1.460-1.465, Si-H content approx. 1% by weight, epoxy number approx. 0.03, ratio of the 2-phenyl-propyl to the C₁₂-alkyl residues approx 1: 5, no dimethyl-Si groups).

Fleet I

With this finishing agent I, an aqueous finishing liquor is prepared as follows:
60 g / l finishing agent I,
40 g / l of an approx. 60% aminoplast resin solution (contains dimethylol dihydroxyethylene urea etherified with methanol and pentamethylolmelamine in a ratio of 12: 1 and approx. 5% neutral salt),
6 g / l of a 30% zinc nitrate solution (pH approx. 1.0) and 2 g / l 60% acetic acid.

Fleet II

Like fleet I, but instead of finishing agent I, components A 1) to C 1) of the fleet are added separately but in equal amounts.

Fleet III

Like fleet II, but with double the amount of component B1).

Fleet IV (comparison)

Like fleet II, but without component B 1).

Fleet V (comparison)

Like fleet II, but instead of component C 1) the same amount of α, ω -dihydroxy-polydimethylsiloxane (viscosity (20 ° C.) approx. 5000 mPa.s) is used in aqueous dispersion.

equipment

A polyester / cotton jacket Popeline 67/33 (approx. 210 g / m²) was padded with liquors I to V (liquor absorption approx. 65%), then dried at 110 ° C. for 10 minutes and condensed at 150 ° C. for 5 minutes.

The results of the equipment are summarized in the table below, the laundry being the usual 40 ° C. household machine wash and the chemical cleaning (CR) washing in the presence of 2 g / l of a conventional cleaning booster and 2 g / l of water (Fleet ratio 1:10). The measurements were carried out after 5 days of exposure in a normal climate. The oil repellency was carried out according to AATCC 118-1972, the water repellency according to DIN 53888 (a = water absorption in%; b = water repellency) and the spray test according to AATCC 22-1974.

Example 2

The following constituents are stirred together to produce the equipment II or II a:

Part A 2)

40 parts of a formulation according to Example 1 of PCT application WO 86/02115 (approx. 6% fluorine).

Part B 2)

10 or 20 parts (II or II a) of a commercially available, nonionic, finely divided, aqueous 21% polyethylene wax dispersion (25% tallow fatty amine ethoxylated with 8 mol ethylene oxide, based on polyethylene wax, as an emulsifier; polyethylene wax with a density of approx. 0.96 g / cm³ at 20 ° C, acid number 27 and saponification number approx. 52).

Component C 2)

40 parts of a 15% aqueous soft handle extender emulsion of an addition product of n-hexadecene (α-olefin with an average of 16 carbon atoms) of methyl hydrogen polysiloxane (molar ratio 1: 2) prepared in accordance with US Pat. No. 4,004,059 (reaction in butyl acetate for a total of 1.5 hours; inactivator: tertiary hexadecyl mercaptan; emulsification as described).

The following aqueous liquors are prepared with the finishing agents II and II a:
90 or 100 g / l of finishing agent II or IIa, 30 g / l of a 60% aqueous solution of pentamethylolmelamine trimethyl ether, 6 g / l of the catalyst solution mentioned in Example 1 and 2 g / l of 60% acetic acid ( Fleets I and II).

The textile material described in Example 1 is finished with the two liquors produced and the following effects are obtained, a comparison based on the prior art (Fleet III with 80 g / l of an agent from A 2) and C2), ie without polyethylene dispersion) was also added.

Example 3

A cotton fabric (170 g / m²) is soaked in an aqueous liquor which contains the following constituents, squeezed to a liquor absorption of about 70%, dried briefly at 105 ° C. and condensed for 5 minutes at 155 ° C.
40 g / l Asahi Guard AG 310 (dispersion based on perfluoroalkyl acrylate polymer with about 9% fluorine), 15 g / l of the polyethylene wax dispersion described in Example 1 (polyethylene wax with d (20 ° C.) = 0.93, acid / saponification number = 16), 20 g / l of a 25% nonionic dispersion of a soft handle extender (H-functional methyl-C₁₀₋₁₂-alkylpolysiloxane with 11 mol% Me-Si-H groups and 89 mol% Me-Si-alkyl- Groups, a viscosity at 25 ° C of 930 mPa.s and n _D 25 = 1.453), 20 g / l of an aqueous, about 50% solution of pentamethylol-melamine methyl ether,
20 g / l of a 45% aqueous solution of dimethylol dihydroxyethylene urea,
2 g / l 60% acetic acid and
8 g / l magnesium chloride hexahydrate (fleet I).

In comparison to the prior art, a liquor is prepared without the polyethylene wax dispersion (liquor II).

With the equipment according to the invention, a fabric with an equally very good and permanent oil and water repellency and a really pronounced soft-hand effect is obtained. According to the state of the art, the effects and especially the grip are less pronounced. Details can be found in the table below:

If, in place of the aminoplast / catalyst system, a conventional sliding firming agent based on polysilicic acid / basic aluminum chloride (active substance approx. 16%) is added to this liquor I in amounts of 15 g / l, the sliding resistance is improved at the same time if, for example, a polyester knitted fabric is equipped.

Example 4

In the same way as described in Example 1, the following two silicones can also be used to prepare component C):

The effect level of corresponding equipment corresponds to the values given in example 1.

Example 5

The fabric described in Example 1 is immersed in a liquor of the following composition, squeezed to a liquor absorption of 55%, dried and condensed at 160 ° C. for 3 minutes:

32 g / l R _f acrylate copolymer (cationic dispersion based on the acrylate of C₆₋₁₀-perfluoroalkyl-N-ethyl-N-β-hydroxyethyl-sulfonamide with approximately 10% fluorine content), 15 g / l of a 27% polyethylene wax dispersion ( Polyethylene wax with d = 0.98 (20 ° C), acid number 25, saponification number 50; 50%, based on polyethylene wax, an emugator mixture of C _16/18 fatty alcohol ethoxylated with an average of 40 moles of ethylene oxide per mole of alcohol and emulsifier according to Example 1 US-A-3,904,661 in the ratio 1: 9) and 20 g / l of component C 1) from example 1 of the present application with the modified hydrogenalkylpolysiloxane from example 1 of US-A-4,625,010 as a soft-grip extender (fleet I).

As a comparison according to the prior art, the same equipment is carried out without the polyethylene wax dispersion (Fleet II).

The washing and cleaning resistance is given in the same way as in the other examples.

Claims (13)

1. Process for conferring a soft water/oil-repellent finish on fiber materials, in particular on textiles, characterised in that an aqueous liquor containing a treatment composition based on perfluoroaliphatic compositions and extenders, the treatment composition having the following composition (sum 100%):

   A) 25 to 65% by weight, relative to the treatment composition, of a water/oil-repellent containing perfluoroaliphatic groups and at least 5% by weight of fluorine in dispersion,

   B) 10 to 35% by weight, relative to the treatment composition, of a 20 to 35% strength dispersion of an emulsifiable polyethylene having a density (at 20°C) of at least 0.92 g/cm³ and an acid number of at least 5 and

   C) 25 to 40% by weight, relative to the treatment composition, of a 25 to 40% strength fluorine-free dispersion of a soft-handle extender based on a modified hydrogenalkylpolysiloxane

   is applied to the material, and said material is finished in the usual manner.
2. Process according to Claim 1, characterised in that mixtures of water/oil-repellents containing perfluoroaliphatic groups are used as component A).
3. Process according to Claims 1 and 2, characterised in that

   - polyurethanes containing perfluoroaliphatic groups,

   - N-methylol condensation products containing perfluoroaliphatic groups,

   - polycarbodiimides containing perfluoroaliphatic groups and/or

   - polymers or copolymers containing perfluoroaliphatic groups are used in the form of a dispersion individually or in a mixture as component A).
4. Process according to Claims 1 to 3, characterised in that the agents containing perfluoroaliphatic groups in component A) contain 5.5 to 15% by weight of fluorine, relative to the dispersion.
5. Process according to Claims 1 to 4, characterised in that the emulsifiable polyethylene in component B) has a density of 0.95 to 1.05 g/cm³, an acid number of 10 to 60 and a saponification number of 15 to 80.
6. Process according to Claims 1 to 5, characterised in that the emulsifier content in component B) is at least 3% by weight, in particular 8 to 40% by weight, relative to the polyethylene wax.
7. Process according to Claims 1 to 6, characterised in that 20 to 35% by weight of component B) is contained in the treatment composition.
8. Process according to Claims 1 to 7, characterised in that mixtures of silicone-based soft-handle extenders are used as component C).
9. Process according to Claims 1 to 8, characterised in that

   - an H-functional C₈₋₁₈-alkylmethylpolysiloxane and/or

   - H-and epoxy-functional C₈₋₁₈-alkylmethylpolysiloxane, each of which, if desired, may contain aryl groups,

   are used in the form of a dispersion as component C).
10. Process according to Claims 1 to 9, characterised in that 25 to 35% by weight of component C) is contained in the treatment composition.
11. Process according to Claims 1 to 10, characterised in that an aqueous liquor containing 40 to 100, in particular 50 to 80, g/l of the about 25 to 35% strength by weight treatment composition is used.
12. Process according to Claims 1 to 11, characterised in that additionally 10 to 45 g/l of a commercially available, 40 to 60% strength by weight amino resin are used.
13. Process according to Claims 1 to 12, characterised in that furthermore customary textile auxiliaries are used in a known manner.